Rubber-like multipolymers of butadiene hydrocarbons, vinylidene chlordie, and acrylic compounds



Patented Feb. 5, 1946 DIENE HYDROCARBONS,

CHLORIDE, AND

16 Claims.

This application is a continuation-in-part of my copending application Serial No. 346,657 filed July 20, 1940, and relates to new synthetic rubber-like materials and to the method of preparing the same.

It has long been the desire of workers in the art of synthetic rubber-like materials to produce a synthetic rubber which would resemble natural rubber in possessing excellent plasticity, tackiness and ease of processing when unvulcanized and in being capable-of vulcanization to a strong elastic condition, and at the same time would excel natural rubber in those properties, such as resistance to oils, to heat, and to oxidation,

in which natural rubber is deficient. Such a synthetic rubber would be able to serve not only as a replacement for natural rubber but also in new applications in fields where natural rubber cannot be used.

The synthetic rubbers which have heretofore been prepared, however, have generally been found to be lacking in one or more of these desired characteristics. Thus, for example, the synthetic rubber produced by copolymerizing butadiene-l,3 and a lesser amount of acrylonitrile is much more resistant to oils than is natural rubher but, on the other hand, is much less plastic and tacky and can be processed only with difliculty. Similarly, other proposed synthetic rubbers prepared by copolymerizing butadiene-LB with other acrylic compounds or by copolymerizing butadiene-1,3 with vinylidene chloride have also been found to be lacking in the desired properties. l

I have now discovered a new class of synthetic rubbers which are plastic, tacky, easily worked and easily processed in the unvulcanized state "INYLIDENE ACRYLIC COMPOUNDS Frank K. Schoenfeld, Silver Lake, Ohio, assig'nor to The B. F. Goodrich Company, New York, N. Y., a. corporation of New York No Drawing. Application July 24, 1943, Serial No. 496,068

and which are also exceptionally-strong, resilient and resistant in the vulcanized condition. Furthermore, as will hereinafter appear,theypossess other valuable properties which make them especially useful in a number of specializedapplications.

These new synthetic rubbers are polymeric ma terials, termed herein multipolymers because they are derived from at least three polymerizable constituents, and are prepared by thepolymerizaticn of a mixture of at least three polymerizable materials, one of whichis'a butadi'ene-L? hydrocarbon, another of which is vinylide'ne chloride and a third of which is a polymerizable acrylic compoundfthe butadiene-1,3 hydrocarbon component being present in the mixture to an extent of at least 50% by weight.

The term "butadiene-L3 hydrocarbon? is used wherein; R2 and Rsi aife ihydrogen b 3mm); andX is hydrogen or herein in its ordinary generic sense to include not only butadiene-1,3 itself (commonly called butadiene) but also the hydrocarbon homologs of butadiene-1,3 which polymerize in essentially the same manner such as isoprene, 2,3-dimethyl butadiene-1,3, piperylene, 2-methyl pentadiene 1,3 and the like. All these compounds generally possess the structure tin wherein each R. is hydrogen or an alkyl group.

X CHz=-Y wherein Y is a characterizing group, specifically a carboxylic acid group i v (E nitrile group (G N) ester group i (E-on.

wherein R1 is the radicalof a nonoh'ydric alcohol) or amide group I, W

R3 men ace-lizing substituen't including hydrocarb '1 groups such as alkylandaryl groups halog enjatoms such as chlorine, oxyhydrocarbon group's such v jas alkoxy groups, and halogen and city-"substituted hydrocarbon groups, Typical example s'pifsuch polymerizable acrylic compounds include f. polymerizable acrylic 'fnitriles such 'as .acrylonitrile,

ac lii file methacrylonitrile, ,alpha -ethyl' I alpha-chloro ,acrylonitrile, alpha-methoxy acryloni't rile and the like; polymerizable' acrylic esters such as methyl acrylate, ethyl acrylate, 'n'-butyl acrylate. allyl acrylate, bencyl acrylate, chloroethyl acrylate, methoxy methyl acrylate and the corresponding methacrylates, ethacrylates, al-

pha-chloroacrylates and the, like; polymerizable acrylic amides such as acrylamide and methacrylamide and polymerizable acrylic acids such as acrylic and methacrylic acid. In this inven- Vinylidene chloride and the arcrylic compound,

should be such that at least by weight of each of these materials is present, sinceotherwise a true multipolymer may not be formed. For production of a synthetic rubber which is plastic, tacky and easily processed in the unvulcanized condition and yields strong, resilient, oil-resistant vulcanizates, an especially desirable type of synthetic rubber, it is preferred to employ a mixture consisting of from 50 to 80% by weight of the .butadiene-1,3 hydrocarbon, from to 40% by weight of Vinylidene chloride, preferably from to 30%, and from 10 to 40% by weight of an acrylic nitrile, with a total of 100%. Still more preferably the mixture, in this case, should contain from 65 to 80% by weight of butadiene-1,3, from 15 to 25% by weight of .vinylidene chloride and from 10 to by weight of ac'iyionitrile. Similar ranges of proportions are preferably employed when other acrylic compounds are used.

tion of a synthetic latex of improved properties, it isdesirable to employ as little as 5% of vinylidene chloride and asmuch as 40% of acrylonitrile 4 All these added substances are mentioned only or other acrylic compound; while for still other purposes, for example for improving the yield and increasing the'speed of polymerization, it is sometimes desirable to employ as high. as 40% by weight of Vinylidene chloride and at little as.

'For other purposes, for example for the production such as polymerization in homogenous systorn by the action of heat, light or catalyst may also be employed. In the emulsion polymerization process the mixture or monomers is emulsifled in water by the use of a suitable emulsifying agent to form an aqueous emulsion to which is aded, preferably, one or .more polymerization initiators to start the-polymerization reaction, one or more polymerization accelerators or cataysts to speed up the reaction and one or more polymerization modifiers to improve the quality .of the product. The emulsion is then-agitated at a temperature of about 20 to 80 C. for a time sunlcient to complete the polymerization, or for a time suflicient to convert a desired proportion of the monomers into polymers, say 75%, about 10 to 100 hours usually being required. The

produce a crude synthetic rubber-resemblin crude natural rubber.

Emulsifying agents which may be used in the above process include soaps of fatty acids such as the sodium and potassium salts of lauric, myristic, 'palmitic, oleic or stearic acids, soaps of rosin acids,'and other soap-like materials in.- cluding salts of organic bases containing long carbon chains such as cetyl trimethyl ammonium methyl sulfate, alkali metal hymolal sulfates such as sodium lauryl sulfate, and aryl and 'alkaryl sulfonates such' as sodium isobutyl naphthalene sulfonate and sodium decyl benzene sulfonate.

Polymerization initiators (sometimes called catalysts) which maybe used in the emulsion polymerization process include per-oxygen compounds such as hydrogen peroxide, benzoyl peroxide, potassium persulfate, sodium perborate, potassium percarbonate and the like as well as other types of initiators such as diazoamino benzene and dipotassium diazomethane disulfonate. Polymerization accelerators (also sometimes called catalysts and activators) which may be used include heavy metal salts such as ferrous sulfate, cobalt chloride and the'like, sodium pyrophosphate etc. Polymerizationmodifiers which are also preferably present during the polymerization to improve the plasticity and solubility of the product are usually sulfur-containing organic compounds such as dialkyl dixanthogens, aliphatic mercaptans, the higher tetralkyl thiuram mono, diand polysulfides, the 2-mercapto thiazoles and the like.

Other polymerization initiators, accelerators and modifiers or other substances which enable the polymerization to be carried out in a shorter time and/or which in some manner improve the quality of the products obtained may also be included in the emulsion before polymerization.

polymerized in the absence of these added substances if desired.

The method of preparing the rubber-like multipolymers of this invention and the unexpectedly desirable properties which they have been found to possess may further be illustrated by the following specific examples in which the parts, I

unless otherwise indicated, are by weight,

Example I An emulsion containing the fohowing ingredients is prepared;

Hydrogen peroxide (3%% aqueous solu-;,

tion) 10 Di-isopropyl dixanthogen 0.3 I

The emulsion is then agitated for 24 hours at a f temperature of 40 C. An 87% yield of a rubber-- like multipolymer is obtained. The multipolymer is a soft, coherent, plastic,-tacky material which may easily be worked on a hot or cold mixin mill in the manner customary with natural rub-' her. It is 90% .soluble in benzene. When compounded in a typical test recipe with carbon black, stearic acid, zinc oxide, sulfur and a vulcanization accelerator and then vulcanized, a

vulcanizate is obtained which possesses a tensile strength of about 4,000 lbs/sq. in. and a 450% elongation. It is also resistant to oils and chemicals and withstands the eflects of aging.

When a similar emulsion containing 75 parts of butadiene-1,3 and 25 parts of acrylonitrile is polymerized, the product is a non-plastic, nontacky material which cannot be milled satisfactorily on a hot mill and which is only 37% soluble in :benzene. When vulcanized, this copolymer exhibits properties substantially the same as that of the above-prepared'multipolymer. On the other hand, when a similar emulsion containing 75 parts of butadiene-1,3 and 25 parts of vinylidene chloride is polymerized, the product is a granular non-coherent material not possessing the desired soft rubber-like properties. It similarly is incompletely soluble in benzene. Moreover, in this event, the polymerization requires over 100 hours and only an 80% yield of copolymer is obtained. Additionally the copolymer, when vulcanized, possesses tensile strengths of less than 2,500 lbs/sq. in. and only about a 200% elongation.

Example II Example I is repeated except that the following proportions of polymerizable materials are employed:

Parts Butadiene-La 70 Vinylidene chloride 20 Acrylonitrile r The polymerization requires 43 hours at 30 C.

and produces a 90% yield of a rubber-like multipolymer having properties similar to those of the product described in Example I. When '70 parts of butadiene-l,3 and 30 parts of vinylidene chloride are similarly polymerized, the polymerization requires over 200 hours at 30 C. to produce a. 69% yield of a rubber-like material which possesses far inferior tensile strength and elongation.

Example III A mixture of 55 parts of butadiene-1,3, 38.2 parts of acrylonitrile and 6.8 parts of vinylidene chloride is polymerized in the presence of 200 parts of a 1.5% aqueous solution of an alkyl benzene sulfonate as an emulsifying agent, 0.35 part of hydrogen peroxide as a polymerization initiator, 0.40 part of diisopropyl dixanthogen as a. polymerization modifier and 0.2 part of a catalyst mixture comprising ferric sulfate, cobalt chloride and sodium pyrophosphate. The polyunerization is complete in about 21 hours and the product is a latex-like dispersion resembling natural rubber latex. Films deposited from this latex by the coagulant dip or electrodeposition methods or simply by allowing a small amount of the latex to dry on a glass plate are found to possess excellent properties, that is, they are plastic, tacky and freely flexible yet are tough and possess excellent strength both when wet and dry. A similar latex from 55 parts of butadiene-1,3 and 45 parts of acrylonitrile required 24 hours for preparation and the films deposited therefrom were inferior in properties having inferior plasticity and low wet-film strength. When the above example is repeated using as the polymerizable materials 55 parts of butadiene- 1,3, 40 parts of vinylidene chloride and 5 parts of acrylamide, a similar latex from which excellent films may be deposited is obtained. However, a latex prepared from butadiene-1,3 and vinylidene chloride alone is not suitable for the deposition of strong tough films.

' Example IV A mixture of parts of butadiene-1,3, 20 parts of methyl acrylate and 20 parts of vinylidene chloride is polymerized in an aqueous emulsion in the presence of 250 parts of a 5% solution of a fatty acid soap, 0.3 part of potassium persulfate and 0.3 part of lauryl mercaptan. The resulting synthetic rubber-is completely soluble in benzene and acetone and from it cements of high tack which are useful in a number of applications as adhesives, is obtained, Similar synthetic rubbers from butadiene-L3 and methyl acrylate or from butadiene-l,3 and vinylidene chloride are not so well suited for this purpose.

, The above specific examples have been cited only for purposes of illustration and it is not intended that the invention be limited solely thereto for it is to be understood that variations in the nature and proportions of materials polymerized and in the'polymerization conditions, in accordance with the above disclosure, may be effected therein without departing from the spirit and scope of the invention as defined by the appended claims.

I claim:

1. The process which comprises polymerizing a mixture of monomeric materials comprising at least 50% by weight of a butadiene-1,3 hydrocarbon, at least 5% by weight of vinylidene chloride and at least 5% by weight of a polymerizable acrylic compound containing a single olefinic double bond linking a methylene (CH2) group and a carbon atom.

2. The process which comprises polymerizing in aqueous emulsion a mixture of monomeric materials comprising from 50 to 80% by weight of a butadiene-LB hydrocarbon, from 10 to 40% by weight of vinylidene chloride and from 10 to 40% by weight of a polymerizable acrylic compound containing a single olefinic double bond linking a methylene (CH2) group and a carbon atom.

3. The process which comprises polymerizing in aqueous emulsion a mixture of monomeric materials comprising from 50 to 80% by weight of a butadiene-1,3 hydrocarbon, from 10 to 40% by weight of vinylidene chloride and from 10 to 40% by weight of a polymerizable acrylic nitrile containing a'single olefinic double bondlinking a methylene (CH2) group and a carbon atom.

4. The process which comprises polymerizing in aqueous emulsion a mixture of monomers consisting of at least 50% by weight of butadiene- 1,3, at least 5% by weight of vinylidene chloride and at least 5% by weight of acrylonitrile.

5. The process which comprises polymerizing in aqueous emulsion a mixture of monomers consisting of to by weight of butadiene-1,3, 15 to 25% by weight of vinylidene chloride, and 10 to 20% by weight of acrylonitrile.

6. The process which comprises polymerizing in. aqueous emulsion a mixture of monomeric materials comprising from 50 to 80% by weight of a butadiene-l,3 hydrocarbon, from 10 to 40% by weight of vinylidene chloride and from 10 to 40% by weight of a polymerizable acrylic ester containing a single olefinic double bond linking a methylene (CH2) group and a carbon atom.

7. The process which comprises polymerizing in aqueous emulsion amixture of monomeric materials comprising from 50 to 80% by weight of butadiene-1,3, from 10 to 40% by weight of vinylidene chloride and from 10 to 40% by weight of a polymerizable alkyl ester of acrylic acid 4 a,eo4,4oel I containing a. single oleflnic double bond linking 12. A rubber-like multipolymer prepared by a. methylene (CH2) group and a carbon atom. the method of claim 4.

8. The process which comprises polymerizing 13. A rubber-like multipolymer prepared by I in aqueous emulsion a mixture of monomers the method of claim 5. consisting of 50 to 80% .by weight of butadiene- 5 14. A rubber-like multipolymer prepared by 1,3, 10 to 40% by weight of vinylidene chloride the method of claim 6.

and 10 to 40%. by weight of methyl acrylate. 15. A rubber-like multipolymer prepared by 9. A rubber-like multipolymer prepared by the the method of claim 7.

method of claim 1. 16. A rubber-like muitipolymer prepared by 10. A rubber-like multipolymer prepared by the method 01' claim 8.

the/method of claim 2. ANK K. SCHOENFEI D,

11. A rubber-like multipolymer prepared by the method of claim 8. v 

